Omicron, omicron, omicron-trisubstituted phosphorothioates



nited States Patent Ofice 3,391,228 Patented July 2, 1968 ABSTRACT OF THE DISCLOSURE Surfactants having the following formula:

[R0(RO)ml(CH2CH20)n]3P S wherein R is hydrocarbyl and hydrocarbyl acyl and R is hydrocarbyl.

This invention relates to new and novel surfactants (surface active agents) as well as a process for their manufacture and more particularly to 0,0,0-trisubstituted phosphorothioates derived from organic polyoxyalkylene ethers and a process for their manufacture.

An object of this invention is to provide a new and novel class of surfactants, the ODD-trisubstituted phosphorothioates having as substituents organic polyoxyalkylene ethers. Another object of the present invention is to provide an improved process for the preparation of 0,0,0-trisubstituted phosphorothioates that does not involve use of solvents or purification of intermediates or products. These and other objects of this invention will become apparent as this description proceeds.

The objects of this invention are attained by our discovery that a new class of 0,0,0-trisubstituted phosphorothioates which have organic polyoxyalkylene ethers of the type used as nonionic surfactants (surface active agents) as snbstituents are obtained in quantitative yields by a process is illustrated by Equation 1 wherein R is a radical containing from 6 to 43 carbon atoms and is a radical selected from the class consisting of alkyl radicals, aryl radicals, alkylaryl radicals, alkylarylmethylene radicals and acyl radicals, R is a divalent residue of a vicinal epoxide containing from 2 to 12 carbon atoms, m is an integer of from 1 to 150, n is an integer of from 1 to 150, the sum of ml and n is from 1 to 150, and R and R each represents a residue of an organic polyoxyalkylene ether of the formula:

determined by iodometric titration of a sample from the reaction mixture to determine the percent unreacted phosphite. If the sample shows unreacted phosphite is not present, reaction is complete.

Trisubstituted organic oxyalkylene ether phosphites which may be used in the process disclosed in this invention include those phosphites which may be represented by Formula I:

wherein R, R m and n have the values assigned above and R and R" each may be alike or different and represents a member selected from the group wherein R, R m and 11 also have the values assigned above. Trisubstituted phosphites as represented by Formula I and methods for their preparation are disclosed in the copending application of Schenck, Leary, Nunn and Huber, Ser. No. 333,701 filed Dec. 26, 1963 now abandoned, and in the copending application of Nehrnsmann, Nunn and Schenck, Ser. No. 275,222 filed Apr. 24, 1963 now Patent No. 3,277,217 issued Oct. 4, 1966. Triaryl phosphites useful in the preparation of these trisubstituted organic oxyalkylene ether phosphites include among others triphenyl phosphite, tri (o-cresyl) phosphite, tri (m-cresyl) phosphite, tri (p-cresyl) phosphite, tri (2,4- xylenyl) phosphite, tri (2,4-dichlorophenyl) phosphite, tri (hexylphenyl) phosphite, tri (nonylphenyl) phosphite, tri (dinonylphenyl) phosphite, tri (dodecylphenyl) phosphite, tri (2-naphthyl) phosphite, cresyl hexylphenyl phenyl phosphite, their isomers, their mixtures or the like. The complete disclosures and teachings of both of these copending applications are incorporated herein by reference.

Any form of elemental sulfur such as flowers of sulfur, roll sulfur, brimstone, sulfur flour, liquid sulfur or the like may be used. In general, flowers of sulfur or liquid sulfur is used, and refined grades having a purity of not less than 99.8% are employed.

We have discovered that these new phosphorothioates are useful as surfactants. They are low foaming surfactants which have low rewetting values and are useful as surfactants in applications where rewetting is not desirable. This new class of surfactants also has the advantage that even though they contain sulfur, they do not have objectionable odors.

As examples of polyoxyalkylene ethers of organic compounds which may be used in the production of trisubstituted phosphites for use in the process disclosed in this invention, those which are normally employed commercially as nonionic surfactants (surface active agents) are preferred. Nonionic surfactants are well known in the art and have many commercial uses. Such nonionic surfactants may be represented by Formula II wherein R is an alkyl radical containing from 6 to 28 carbon atoms, an aryl radical containing from 6 to 14 carbon atoms, an alkylar-yl radical containing from 7 to 42 carbon atoms, an arylmethylene (benzyl) radical con taining from 7 to 43 carbon atoms, an alkylarylmethylene (alkylbenzyl) radical containing from 8 to 43 carbon atoms, or an acyl radical containing from 6 to 30 carbon atoms, R is the divalent residue of a vicinal epoxide conlllll .32

taining from 2 to 12 carbon atoms. in lS .lll integer or from 1 to 150, n is an integer of from to 50 and the sum of m-1 and n is from i to lSO.

In Formula II, R may be either a straight or branched chain alkyl radical containing from 6 to .18 carbon atoms such as hexyl, octyl, nonyl, decyl, henadecyl. uinonyl, dodecyl, tridecyl, tetradecyl. hexadecyl. heptadecyl. octadecyl, nona-decyl, eicosyl. heneicosyl, tiocosyl, tricosyt. tetracosyl, pentacosyl, hexacosyl, heptacosyl. JlVl'lCYl. their isomers, their mixtures or the like. R may 1150 06 an aryl radical of from I5 to l4 carbon atoms men as phenyl, diphenyl, naphthyl, 2- and S-anthryl or the like. Likewise, R may be an alkylaryl radical containing from 7 to 42 carbon atoms such as tolyl lrnethylphenyl). ethylphenyl, propyl-phenyl. butylphenyl, diamylphenyl. actylphenyl, nonylphenyl, decyl-phenyl, dodecylphenyl. tetradecylphenyl, pentadecylphenyl, octadecylphenyl, dinonylphenyl, dioctadecylphenyl, their isomers, their mixtures or the like. R may also be an ary-lmethylene tbenzyl) radial or an alkylarylmethylene radical containing from 7 to 43 carbon atoms such as benzyl, methylbenzyl. nonylbenzyl, diamylbenzyl, didodecylbenzyl. octadecylbenzyl, dioctadecylbenzy-l. their isomers. their mixtures or the like. R may be an acyl radical of from 6 to 30 carbon atoms derived from an organic acid such as caproic. caprylic, pelargonic. capric. n-undecylic. lauric. tn ristic. palmitic, margaric, stearic, nrachidic, behenic. lignoceric. cerotic, melissic, oleic, elaidic, linoleic. m-eleostearic. releostearic, a-linolenic. erucic acid, their isomers or the like.

Suitable methods for preparation of these nonionic surfactants are described in US. Patents 5.970.578: 2,213,477; 2,575,832; 1.593.112; and 1.676.975. The complete disclosures and teachings of these patents are 1ncorporated herein by reference. in the preparation or these surfactants, straight or branched chain alkyl alcohols, aryl alcohols, or arylmethyl alcohols. .ll'ld their alkylated derivatives or aliphatic acids may be reacted with the vicinal epoxide either single or in combination with each other.

Suitable vicinal epoxides for use in preparation of these nonionic surfactants include those compounds which can be represented by Formula III III) wherein the radicals designated as R R R and R individual-1y can be hydrogen and alkyl. alkenyl. arvloxv alkyl, oh the like groups, and two of the radicals d681,!- nated as R R R and R may be taken together to form a cycloalkyl group. preferably wherein the said groups have from 1 to 10 carbon atoms. Thus in Formula II above, the radical R which represents the divalent residue of a vicinal epoxide, can be represented by Formula 1V (IV) R B t it .ipoxycyclohexane and alkyl-substituted epoxycyclohexmes. cpoxycyclopentane and alkyl-substituted epoxycy- .ziupentanes. .LJ-epoxybicyclo (2.2.1) heptane, or the like. Preferred vicinal epoxides include alkylene oxides such as ethylene oxide, l,2-epoxypropanc, the epoxybutanes, ll the like. Thus, in one preferred embodiment of the inention. when an alkylene oxide is employed, Formula A l can be represented as C. H wherein a has a talue or" from 3 to 12.

When nonlonics are produced by reaction with vicinal tpoxidcs containing more than 2 carbon atoms, these surfactants should be reacted with at least 1 mole of ethylene .lXldG per mole of nonionic surfactant before they are employed in the present invention so that the polyoxy- .ilkylene chain lS terminated with a hydroxyl attached to the divalent residue of an ethylene oxide molecule. the number of moles of ethylene oxide which may be tised in he manufacture of these nonionic surfactants may vary trom l to 150 moles per mole of hydroxylic compound tphenol, aliphatic acid or alcohol compound),

t ts examples of hydroxylic compounds which may be llsed in the process disclosed by this invention, there may tile mentioned these polyoxyalkylated derivatives of phenol and alkylphenols in which the total number of alkyl carbon atoms on the phenol molecule is from 1 to 36, those tlerivatives of aliphatic alcohols containing from 6 to 28 carbon atoms as well as those of benzyl alcohol and tilkylbenzyl alcohols in which the total number of alkyl the total number of carbon atoms is from 6 to 30.

a ts examples of such alkylphenols there may be mentioned hexylphenols, heptylphenols, octylphenols, nonylylllilenOlS. decylphenols, dodecylphenols, tridecylphenols, rt-ctadecylphenols. their mixtures or their isomers. The polyoxyalkylated derivatives of secondary alkylphenols llbtailmd by aikylation of phenols or cresols with a-olefins at the types obtained by the condensation of ethylene in he presence of Ziegler type catalysts or by wax cracking techniques are of particular value. u-Olefins useful in the treparation or these alkylphenols may contain odd or ttven numbers of carbon atoms. Mixtures of ot-olefins having various ranges of carbon atoms such as C -C C -C t C if -C C11 15y C C and higher may be used ll. the preparation of these alkylphenols. Olefins containing even numbers of carbon atoms such as those derived mm fats may be employed. Alkylphenols such as m-penttrlecylphenols may also be used. The polyoxyalkylated .terivatives of alkylphenols obtained by alkylation of pherot or cresol with dimers. trimers, tetramers, or the like of lower molecular weight olefins, such as propylene, butylthe, arnytene. their isomers or their mixtures may also be lSBCi. Likew1se. diand tri-substituted alkylphenols obtained by alkylation of the above-mentioned alkylphenols may be used. As examples of such di and trialkylphenols, there may be mentioned nony-lcresol, diamylphenol, ditlocylphenol. dinonylcresol, tri-t-butylphenol, trinonylittenol, di-octadecylphenol or the like.

The polyoxyalkylene ethers of alcohols containing from i to 28 carbon atoms are another preferred group of nonlODlC surfactants which may be employed in the producion of trisubstituted phosphites in the present invention. These include the polyoxyalkylene ethers of hexyl alcolllllli. octyl alcohol, decyl alcohol, dodecyl alcohol, tridecyl ricohol. hexadecyl alcohol, octadecyl alcohol, docosyl alcohol. heptacosvl alcohol, myricyl alcohol, their isomers, llhfill' mixtures or the like. Ethers of secondary alcohols tuch as IZ-octanol, E-tetradecanol, 2-hexadecanol or the like may also be used. Alcohols useful in the preparation bf these ethers may be produced by a variety of methods. For example, they may be prepared by the hydrogenation iif fatty acids or glycerides. They may be prepared by the ttxo process. They may also be prepared by the Ziegler gtrocess as described in Kirk-Othmer, Encyclopedia of tihemical Technology, vol. 1, p. 540 (John Wiley & Sons, New York I l?!" .1 cd.,, l963).

.ziarbon atoms is from 1 to 36 and aliphatic acids in which Benzyl alcohol and alkylbenzyl alcohols in which the total number of alkyl carbon atoms is from 1 to 36 may also be used in the preparation of nonionic surfactants which may be converted to trisubstituted phosphites for use in this invention. Specific examples of benzyl alcohols which may be employed include among others, benzyl alcohol, p-methylbenzyl alcohol, o-ethylbenzyl alcohol, propylbenzyl alcohol, i-propylbenzyl alcohol, t-butylbenzyl alcohol, s-pentylbenzyl alcohol, n-hexylbenzyl alcohol, octylbenzyl alcohol, nonylbenzyl alcohol, dodecylbenzyl alcohol, tridecylbenzyl alcohol, octadecylbenzyl alcohol, their isomers, their mixtures or the like.

The polyoxyalkylene ethers of organic acids in which the total number of carbon atoms in the acid is from 6 to 30 are another group of nonionic surfactants which may be employed in production of trisubstituted phosphites for use in the present invention. This group includes the polyoxyalkylene ethers of caproic acid, caprylic acid, pelargonic acid, capric acid, n-undecylic acid, lauric acid, myristic acid, palmitic acid, margaric acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, cerotic acid, melissic acid, oleic acid, elaidic acid, linoleic acid, a-eleostearic acid, B-eleostean'c acid, a-linolenic acid, erucic acid, their isomers or the like.

The following examples of nonionic surfactants may be employed in the manufacture of trisubstituted phosphites for use as intermediates in the process described by this invention. In these examples, E.O. represents ethylene oxide, Pr. 0. propylene oxide, Bu. 0. butylene oxide, c. 0. octylene oxide, St. 0. styrene oxide, Dd. 0. dodecylene oxide, and the number immediately preceding each of these formulas refers to the number of moles of the oxide thereof reacted with one mole of the reactive hydrogen containing organic compound. Such nonionic surfactants include phenol+1E.O., phenol+5Bu.O.+ 1E.O., o-cresol+1Pr.O.+2E.O., diisobutylphenol+9E.O., nonylphenol+6E.O., diamylphenol+8E.O., dodecylphenol+2E.O., diamylphenol+1St.O.+10E.O., hexylphenol+4E.O., octadecylphenol+20E.O., dioctadecylphenol+150E.O., lauryl alcohol+4E.O., isooctyl alcohol (oxo alcohols)+5E.O., decyl alcohol (oxo alcohols)+ 50Pr.0+100E.O., tridecyl alcohol (oxo alcohols)+ 50E.O., tallow alcohol-l-3OE.O., stearyl alcohol+70E.O., t-butylphenol+10c.O.+18E.O., phenol+1Dd.O|-12E.O., n-hexyl alcoh0l+1St.O+11E.O., lauryl alcohol (Ziegler process)+Pr.O.+20E.O., oleyl alcohol+40E.O., mpentadecylphenol+90E.O., methyl alcohol+1E.O., acetic acid+1E.O., oleic acid+15OE.O., dichlorophenol+3E.O., chlorobutanol-l-ZEO. and stearic acid+13E.O., or the like.

It is to be understood that in some applications use of I nonionics derived from mixtures of alkylphenols or alcohols may be beneficial. Such mixtures may include alkylation mixtures containing alkylphenols and unreacted olefins, alkylphenol mixtures which have been stripped to remove unreacted olefins, residues of alkylation mixtures containing high boiling alkylphenols, crude alcohol mixtures, alcohol mixtures containing dissimilar alcohols, mixtures of alcohols and phenols or the like. Advantages of these compositions as hydrophobes for nonionics are well known to those skilled in the art. Frequently, such mixtures have unique and improved surfactant properties. As further examples of such compositions which may be used to prepare polyalkoxylated derivatives, there may be mentioned mixtures of nonylphenol, still bottoms from dodecylphenol alkylations, crude alcohol mixtures obtained from hydrogenation of natural products such as vegetable or animal oils or alkoxylated mixtures obtained from the commercial synthetic alcohol processes.

The following examples illustrate preferred embodiments of the process disclosed by this invention. These examples are only illustrative of the invention and are not to be regarded as limitative. It will be understood that all parts, percentages and proportions referred to herein and in the appended claims are by weight unless otherwise indicated.

Example 1 Tri (nonylphenol+9 E.O.) phosphite, 500 g. (0.27 m.) is charged to a 1-liter 4-neck flask equipped with thermometer and agitator. The charge is heated C. and 8.65 g. sulfur (0.27 m.) is added with agitation over 5 minutes. This reaction mixture is stirred for 30 minutes or until all of the sulfur is reacted. Analysis shows that the product does not contain any unreacted phosphite ester and that the product is 0,0,0-tri (nonylphenol+9 E.O.) phosphorothioate. The product has a surface tension at 0.1% of 38.3 dynes/cm. at .01% of 42.2 dynes/cm. and at .001% of 46.9 dynes/cm. At a concentration of .05 the product has a Ross Miles Foam of 15 mm. at 0 minutes and 10 mm. after 5 minutes. At a concentration of 0.1%, the product has a Draves Wetting of over 300 seconds at 25 C. and 252 seconds at 70 C. The trisubstituted phosphites used in this example and the following examples are prepared by the method disclosed in copending application Ser. No. 333,701, filed Dec. 26, 1963.

Example 2 Tris (oleyl alcohol+7 E.O.) phosphite, 500 g. (0.29 m.) and sulfur 9.3 g. (0.29 m.) are charged into a 3-neck l-liter flask equipped with an agitator and thermometer. This mixture is reacted with agitation at 50 C. for six hours. Analysis of the product by iodometric titration shows that it does not contain any unreacted phosphite ester. A yield of 509 g. of 0,0,0-tri (oleyl alcohol+7 E.O.) phosphorothioate is obtained.

Example 3 Into a flask equipped as described in Example 1, 682 g. (1.0 m.) tris (octyl alcohol+2 E.O.) phosphite and 32.0 g. (1.0 m.) sulfur are charged. This reaction mixture is then stirred at C. for three hours. Analysis shows a yield of 714 g. of 0,0,0-tris (octyl alcohol+2 E.O.) phosphorothioate.

Example 4 Operating as in Example 1, 500 g. (0.024 m.) tris (octadecylphenol+ E.O.) phosphite and 0.77 g. (0.024 m.) sulfur are charged into a l-literfiask equipped with thermometer and agitator. This reaction mixture is stirred at 150 C. for 1 hour. Analysis shows a quantitative yield of 0,0,0-tri (octadecylphenol+150 E.O.) phosphorothioate is obtained. The product has a surface tension of 43 dynes/ cm. at 0.1% concentration in water.

Example 5 Into a 1-liter 4-neck flask equipped as described in Example 1 is charged 674 g. (0.5 m.) tri (nonylphenol+5 E.O.) phosphite and 16.0 g. (0.5 m.) sulfur. The reactants are stirred at 150 C. for 15 minutes. Analysis shows 690 g. of 0,0,0-tri (nonylphenol+5 E.O.) phosphorothioate is obtained. Presence of the thioate radical is verified by sulfur analysis and absence of phosphite by iodometric titration.

Example 6 Operating as in Example 1, a flask is charged with 585 g. (0.64 m.) tris-(o-cresol+2 Bu.O.-|-1 E.O.) phosphite and 20.5 g. (0.64 m.) sulfur. Analysis shows a quantitative yield of 0,0,0-tris-(o-cresol+2 Bu.O.+1 E.O.) phosphorothicate is obtained.

Example 7 Proceeding as in Example 1, 472 g. (.179 m.) of tri- (dinonylphenol-i-IO P.O.+1 E.O.) phosphite is substituted for tri(nonylphenol+9 E.O.) phosphite. A yield of 477.7 g. of 0,0,0-tri(dinonylphenol+10 P.O.+1 E.O.) phosphorothioate is obtained by heating the phosphite with 5.7 g. (0.179 m.) sulfur for one hour at 100 C.

Example 8 A charge of 500 g. (0.27 m.) of tri(dichlorophenol+ 10 E.O.) phosphite and 8.65 g. i0.17 m.l sulfur are aeated at 125 C. with agitation for two hours. A quantitative yield of 0,0,0-tri(dichlorophenol+l0 E.O.l phosphorothioate is obtained.

Example 9 495 g. (0.34 m.) of llauryl alcohol-t-l E0. octylphen0l+3 E.O.) ttridecylalcohol+15 E0.) priosnnite. a trisubstituted phosphite. is charged to a L-iiter tlaslc equipped as in Example 1 and heated to lSO" for one hour with 10.9 g. 0.34 m.) sulfur. Analysis snows a quantitative yield of the corresponding tniophosunatc is obtained and that the product does not contain pnos phites or hydrolysis byproducts.

Example 10 Operating as in Example 1. 585 g. 10.64 m.) or intocresol+2 Bu.O.-l-l E0.) phosphite and 10.5 1. p.64 m.) sulfur are charged. Analysis shows the reaction gives a quantitative yield of tri(o-cresol+2 Bu.O.-l ED. thiophosphate.

0,0,0-trisubstituted phosphorothioates derived from organic oxyalkylene ethers have many useful applications as surfactants. For example, they may be employed as emulsifiers or wetting agents in latices where rewetting is not desired. These esters may also be employed as grinding aids and dispersants for pigments. They may be used as emulsifiers for biocides such as DDT. Parathion. Malathion or the like. These products are also useful as emulsifiers in latex and emulsion paints. They may also be used in combination with other surfactants such as nonionics, anionics and cationics as well as with builders. or fillers (e.g. sodium silicates, sodium phosphates. carbonates, sulfates, borax and the like), solvents and the like in the formulation of products useful as detergents. emulsifiers and dispersants.

This invention has been disclosed with respect to certain preferred embodiments. Various modifications and variations thereof will become obvious to persons SKllled in the art. It is to be understood that such modifications and variations are to be included within the spirit and scope of this invention.

What is claimed is:

1. A surfactant composition having the Formula I radicals, aryl radicals. alkylaryl radicals. benzyl radicals. alkylbenzyl radicals and acyl radicals. R is a divalent t It t? i'esidue or .1 ricinal epoxide containing from 2 to 12 .tarbon atoms. in is an integer of from 1 to 150, n is an integer or from l to [50, the sum of m-l and n is from to l5O and R and R are residues of representative members or the group llto(R O),..-irCIt;CIIz0)..] wherein R. R at and n have the values assigned above.

it. A turtactant composition as defined in claim 1 wherein R :s a nonylphenyl radical, R is a divalent resiilue of an epoxide containing 2 carbon atoms, In is 1, [L l. the sum or .m-l and n is l, R and R are residues .i. the or anic polyoxyalkylene ether shown in Formula t and defined as above.

it. A surfactant composition as defined in claim 1 wherein R is an alkyl radical containing an average of 13 carbon atoms. R is a divalent residue of a vicinal rpoxide containing 2 carbon atoms, m is 1, n is 10, the mum of mi and u is l() and R and R are residues of the organic polyoxyalkylene ether shown in Formula I and defined as above.

t. A aurfactant composition as defined in claim 1 t/herein R is a dodecylphenyl radical, R is a divalent residue of a vicinal epoxide containing 3 carbon atoms, uz is 50. u rs lOl. the sum of ml and n is 150 and R R are residues of the organic polyoxyalkylene ether shown in Formula I and defined as above.

A surfactant composition as defined in claim 1 wherein R is a tridecyl radical, R is a divalent residue at a vicinal epoxide containing 2 carbon atoms, In is 1, i is l3. the sum of ml and n is 13 and R and R are tcsidues ot the organic polyoxyalkylene ether shown in "ormula l and defined as above.

iii. A surfactant composition as defined in claim I havng the formula iiiInCt LO(ClIzCllgOh iutilg o(CHzCHgO)P s i.lHz7O(CH2CHgO) 5 therein C,.l-l, C H is an octylphenyl radical, C H .ti a lauryl radical and C H is a tridecyl radical.

illusolapolf. Organophosphorus Compounds, J. Wiley it Sons. lnc.. New York (1950), pp. 2356.

ill'lS .003

Ql-IARLES B. PARKER, Primary Examiner.

t. SUTTO. .lssismnt Examiner. 

